Colorant compatible synthetic thickener for paint

ABSTRACT

A synthetic polymer has a water-soluble or water-swellable polymer backbone and terminal groups and/or intermediate groups of blocks of hydrophobes of alkyl- or aryl compounds containing a polymerizable cyclic monomer or a polymerizable double bond (or alkene) group or derivatives thereof. The blocks of hydrophobes are composed of two or more units of the same or different hydrophobes. These synthetic polymers are used as rheology modifiers, especially in latex paints.

This application claims the benefit of U.S. Provisional Application No.60/534,873, filed Jan. 8, 2004.

FIELD OF THE INVENTION

This invention relates to paint compositions using colorant compatiblesynthetic thickeners. More specifically, the invention relates to theuse in paint compositions a synthetic thickener with a water-soluble orwater-swellable polymer backbone that has terminal groups of hydrophobesof oligomers of alkyl- or aryl compounds containing a polymerizablecyclic monomer (i.e., an epoxide, a glycidyl ether, a cyclic oxide, anoxazoline) or a polymerizable double bond (i.e., styrene, vinyl ether,acrylamides, acrylates), or derivatives thereof.

BACKGROUND OF THE INVENTION

Hydrophobically modified water-soluble polymers of various types havebeen used to thicken latex paints to provide a certain performanceduring manufacturing, storage, and applications. Some of theseproperties include: ease of formulation, pigment settling prevention,film build during application, spatter resistance, low sag, good flow,and leveling of the paint film. These water-soluble polymers may comefrom a natural source like cellulose, starch, polydextran, guar gum ortheir ionic and non-ionic derivatives (hydroxy ethyl, hydroxypropyl).Some examples of synthetic water-soluble polymers are thepolyacrylamides, polyacrylates, polyvinyl alcohol, polyvinyl sulfonates,polyethylene imine, polydadmac, polyamideazetidinium ion,polyvinylpyrolidone, polyaspartates, polyacetalpolyether,polyalkylethers, and polyalkylthioethers. Most of the water solublepolymer types are described in “Water soluble polymers” by Yale Meltzer(Noyes Data Corporation, Parkridge, N.J., USA, 1981).

The hydrophobe attachment is usually done with a single alkyl group oran alkyl phenol ethoxylate bearing a halide or an epoxide. There arealso examples where the hydrophobe is bunched together before theattachment as in U.S. Pat. No. 4,426,485, U.S. patent application Ser.No. 0045724 A1 (2002), U.S. Pat. Nos. 5,292,828, and 6,337,366. In thesepatents, the hydrophobes are pre-connected with each other via aconnecting reagent such as diisocyanate, diepoxide, epichlorohydrin or aprimary amine.

SUMMARY OF THE INVENTION

The present invention is directed to a polymer composition comprising awater soluble or water swellable synthetic polymer backbone that hascovalently connected ends and/or intermediate blocks of oligomerichydrophobes that are selected from the group consisting of i) alkyl andaryl moieties containing a polymerizable cyclic monomer, ii) apolymerizable double bond, and iii) derivatives of i) and ii), whereinthe blocks are two or more units of the same or different hydrophobes.

The present invention also comprehends a process for preparing the watersoluble or water swellable polymer composition mentioned abovecomprising

-   -   a) reacting a water soluble or water swellable backbone polymer        with a catalyzing agent in order to activate the polymer        backbone,    -   b) adding the oligomerizing hydrophobic monomer(s) to the        reaction mass, and    -   c) polymerizing the reaction mass at sufficient temperature and        for a sufficient time in order to add the oligomerizing        hydrophobic monomer(s) to the backbone either as end groups or        intermediate groups.

This invention also relates to an aqueous protective coating compositioncomprising (a) the above mentioned polymer composition, (b) a colorant,and (c) a film forming latex, wherein the viscosity of the aqueousprotective coating composition remains unchanged or has an insignificantloss as compared to when using conventional rheology modifiers uponadding the colorant.

DETAILED DESCRIPTION OF THE INVENTION

A new class of hydrophobically modified water-soluble/water dispersiblepolymers has been found that provide good thickening, leveling, and sagproperties in waterborne coatings that can be used alone without otheradditives in the coating formulation needed in the past for tailoringthe formulation for balancing these properties. It has been found thatall that is necessary is to provide synthetic, water soluble polymericbackbone structures with the capacity to be dissolved in water orswellable in water to the degree necessary for the application at handthat has been modified in accordance with the present invention. The newclass of rheology modifiers is a hydrophobically modified polymer thathas a water-soluble or water swellable backbone portion and oligomerichydrophobe portion(s) in the form of blocks of units. The oligomerichydrophobic block has the following chemical architecture:

where:

-   n is an integer from 1-100-   R is an alkyl or aryl group having from 2 carbons to 100 carbons.    The alkyl group may be saturate or unsaturated, cyclic or non    cyclic, linear or branched, or halogenated, i.e., fluorinated,    chlorinated, or brominated. The alkyl and aryl groups may be,    substituted, such as alkylsiloxane, alkylether, arylalkylether,    alkylarylene ether, alkylene ether, alkyl thioether, alkylene    thioether, alkyl amine, dialkyl amine, dialkyl amine oxide, triakyl    ammonium, diaryl amine, dialkyl phosphine, diaryl phosphine, dialkyl    phosphine oxide, diaryl phosphine oxide, dialkyl phosphate and the    like.-   A is a connecting diradical of —O—, —S—, —CH₂—, —O—CH₂—,    —S—CH₂—,—NH—, —NR′—, —NH—CH₂—, —NR—CH₂—, —PR′—, —POR′—(where R′=1 to    12 carbons), polyalkylene ether (Mw=44 to 50000), polyalkylene    isocyanate-HEUR (Mw=100 to 50,000).-   B is a connecting groups of: —CH₂—, —CH₂O—, CH₂S—, —CH₂—NH—,    —CR″H—O—, —CR″H—S—, —CR″H—NH—, and —CH₂NR″—(where R″=1-12 carbons).-   C is a connecting end same as A or a terminating end equal to: —OH,    SH, —NHR′″, —OR′″, —SR′″, and —H.    Several specific chemical structures are shown below to illustrate    this hydrophobe architecture.

In this case, A=—OCH₂—, B=—O—CH₂—, R=—CH₂O—C₈H₁₈ and C=—OH.

In this example, A=—NHCH₂—, B=—O—CH₂—, R=—CH2O—C₈H₁₈ and C=OC₆H₁₃.

In this structure, A=—OCH₂—, B=—OCH₂—, C=—C₆H₁₃ and R=—OC₆H₅.

In this structure, A=Polyalkylene oxide-CH₂—, B=—O—CH₂—, C=—OH, andR=nonylphenoxy.

In this structure, A=—CH₂—, B=—CH₂—, C=H and R=Ph. (note, Ph is a phenylmoiety).

In this structure, A=—CH₂—, B=—CH₂—, C=—H, and R=—O—C₈H₁₇.

These hydrophobe blocks could be synthesized from corresponding alkylglycidyl ether (or thio or amido) by heating with a base or a propernucleophile of choice. Structures 1-4 are products of alkyl glycidylethers. Control oligomerization like atom transfer polymerization,living radical polymerization, cationic polymerization, anionicpolymerization and group transfer polymerization with proper quenchingreagent would yield desired hydrophobe from reactive vinyl monomers suchas styrene, vinyl ether, vinyl ester, acrylate esters, acrylamide ester.Structure 5 and 6 are product examples of control radicaloligomerization and proper end-capping.

The hydrophobe blocks may be connected to the water soluble/waterdispersible polymer via an ether, ester, urethane, amide, amine, imide,or urea, depending of the choice of one who is skilled in the art. Theconnection could be done via a diepoxide, a diisocyanate, a dialkylhalide, diester, or a compound bearing mix reactive groups (for example,epoxyalkylhalide, alkylhalide isocyanate).

The commonly practiced procedure to attach a hydrophobe to a watersoluble/water dispersible polymer bearing reactable hydroxyl groups suchas cellulose derivatives is by heating the cellulose alkaline derivativewith a hydophobe halide or epoxide. One example of this type of reactionis the synthesis of hydrophobically modified hydroxyethyl cellulose(HMHEC). Both an alkyl halide or an alkyl glycidyl ether can be used asa hydrophobe modifier. Therefore, it is possible to convert thehydrophobe of this invention to an epoxide (using epihalohydrin), or anhalogenating reagent like PBr₃ or PCI₅ to form a reactive hydrophobe.

It is more convenient to incorporate this type of hydrophobe to anaddition polymer (vinyl alcohol, acrylamide, acrylates.) via a monomerbearing this hydrophobe. For example, acryloyl ester of this type ofhydrophobe from Structure 4 could be polymerized along with acrylic acidand acrylamide to give the corresponding hydrophobically modifiedalkaline soluble emulsions (HASE).

It is also convenient to make telechelic polyurethane of hydrophobicallymodified ethylene oxide urethane block copolymer (HEUR) using a pre-madehydrophobe. The hydrophobe containing one hydroxyl or two hydroxylgroups could be added to a mixture of polyethylene oxide with reactivehydroxyl end group then allowed to react with a diisocyanate. It is,however, most convenient to make the HEUR backbone and heat theresultant oligomers with an alkyl glycidyl ether of choice. The alkylglycidyl ether moiety oligomerizes at the end of the HEUR backbone togive the telechelic HEUR.

It is most convenient to just heat a mixture of polyethylene glycol andan alkyl glycidyl ether in the presence of a base in order to makehydrophobically modified PEG. The polymer backbone could be pre-modifiedwith one or several alkyl diols or alkyl triol to form a branchedstructure, or converted to an acetal-polyether as described in U.S. Pat.Nos. 5,574,127 or 6,162,877. The reaction scheme below illustrates theease of synthesis of the telechelic polymer of this type.

The present invention is an associative polymer that has a water-solubleor water-swellable backbone that is a synthetic polymer. This backbonecan be derived from a wide selection of materials such aspolyacrylamides, polyacrylates, polyvinyl alcohol, polyvinyl sulfonates,polyethylene imine, polydadmac, polyamideazetidinium ion,polyvinylpyrolidone, polyaspartates, polyacetalpolyether,polyalkylethers, and polyalkylthioethers. Most of the water solublepolymer types are described in “Water soluble polymers” by Yale Meltzer(Noyes Data Corporation, Parkridge, N.J., USA, 1981). The backbone aloneis not reactive and can be any of the synthetic polymers mentioned aboveas long as the backbone polymer is water soluble or water swellable. Thebackbone becomes a reactive site when the hydrophobes are internallyconnected in the backbone or are pendant from the backbone. Thehydrophobes can also be terminal groups (also known as telechelicgroups) on the backbone. The backbone polymer can be linear or branchedor dendritic in shape (i.e., a configuration where three branches areattached to a single atom such as a carbon atom). When the hydrophobicoligomeric blocks are alkyl and aryl moieties containing a polymerizablecyclic monomer, the total number of carbon atoms in the akyl or arylportions of the hydrophobic oligomeric groups can be from 1 to 100.

The oligomeric hydrophobic blocks of moieties are the reactive sites.The blocks of hydrophobic moieties must have at least two units,preferably at least 3 units, more preferably at least 7 units, and morepreferably 10 units. It should be understood that more that 10 units canbe present in the hydrophobic moieties and that the number of units areonly limited by the feasibility and economics of making such moietybased on the size, structure, steric hindrance, and other chemical orphysical forces acting on the closeness of the units attached in theblocks.

In accordance with this invention the oligomeric hydrophobes can be analkyl or aryl moiety containing a polymerizable cyclic monomer or apolymerizable double bond, or derivatives of these moieties. When thehydrophobe is an alkyl moiety containing a polymerizable cyclic monomer,the alkyl group can have 1 to 40 carbon atoms, preferably 3 to 24carbons, and more preferably 6 to 18 carbons. When the hydrophobe is anaryl moiety containing a polymerizable cyclic monomer, the aryl groupcan have 6 to 40 carbon atoms, preferably 6 to 29 carbons, and morepreferably 7 to 15 carbons. Examples of the polymerizable cyclicmonomers are alkyl glycidyl ethers, aryl glycidyl ethers, arylalkylepoxide, alkyl oxazoline, and aryl oxazoline.

When the hydrophobe is a polymerizable double bond, it can be an alkenemonomer such as styrene and stryenic compounds, vinyl compounds,acrylates and derivatives thereof, norbornenes and derivatives thereof,and alkenes and derivatives thereof, alkenyl siloxanes and derivativesthereof, alkenyl silanes and derivatives thereof, fluorinated andperfluorinated alkenes. Examples of alkenes are ethylene, propylene,butylene, etc.

In accordance with the present invention, the polymer composition has aweight average molecular weight (Mw) with the upper limit of the polymerbeing about 10,000,000, preferably about 1,000,000, and more preferablyabout 100,000. The lower limit of the weight average molecular weight ofthe polymer is about 400, preferably about 1,000, and more preferablyabout 4,000.

One application for this type of hydrophobically modified water-solublepolymer is paint formulation. These paint formulations are latex based,such as acrylic based, vinyl acrylic based or styrene based. It has beenfound that the telechelic polymers of the present invention providebalance properties in various paint formulations. However, unexpectedly,for acrylic paint (SG10 M), the resultant paint also showed excellentviscosity retention upon (VRT) tinting with various colorants. This typeof performance is not seen in the regular hydrophobe polymers alone.

In latex paint formulations, the polymer of the present invention can beused alone or in combination with other conventional prior art rheologymodifiers (or thickeners) such as hydroxyethylcellulose (HEC),hydroxypropyl cellulose (HPC), methylcellulose (MC),carboxymethylcellulose (CMC), methylhydroxy ethylcellulose (MHEC),ethylhydroxyethylcellulose (EHEC), and hydrophobically modifiedhydroxyethylcellulose (HMHEC). The typical latex paint formulations ofthis invention are acrylic based, vinyl acrylic based, or styrene based.These latex-based paints have pigment volume concentration (PVC) of from15 to about 80.

Below are a series of examples showing the synthesis of telechelichydrophobically modified PEG and polyacetal ether and their performancein two paint formulations: SG10 M and UCAR 379G (vinyl acrylic basedpaint). All parts and percentages are by weight unless otherwise stated.

EXAMPLE 1 PEG 20K, 16.4% Addition Level of glycidyl 2 methyl phenylether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch and a heatingmantle, a mixture of 30 g of 20,000 Mw PEG (0.0015 mol) and toluene (80mL) was heated to 60° C. At this temperature, KOH (2.1 g, 0.06 mol, in 3g of water) was added and the reaction mixture was stirred for 1 hr.Glycidyl 2- methyl phenyl ether (5.91 g, 0.036 mole) was added and thereaction temperature was kept at 110° C. for 5 hours. After the reactionis cooled to 60° C., toluene (80 mL) was further added. The solution wasprecipitated into 300 mL of hexane. After filtration and washing withethyl acetate (100 mL×3×) and drying in vacuum, a white powder polymer(33.7 g) was obtained. Nuclear magnetic resonance with hydrogen nuclei(¹H NMR) showed 12% hydrophobe incorporation. The Brookfield viscosityof a 5% aqueous solution of this oligomer was 67,000 cps (BF LV, S-63,0.3 rpm at 25° C.). Paint performance: SG10 M (standard formulation) TE%=0.11, Viscosity Loss upon Tinting (VLT)=−4 KU. For UCAR 379 G, TE%=0.54, VLT=−10 KU.

EXAMPLE 2 PEG 35K, 9.3% Addition Level of glycidyl phenyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch and a heatingmantle, a mixture of 40 g of 35,000 Mw PEG (0.0011 mol) and toluene (80mL) was heated to 60° C. At this temperature, KOH (1.54 g, 0.0275 mol,in 10 g of water) was added and the reaction mixture was stirred for 1hr. Glycidyl phenyl ether (4.12 g, 0.0275 mole) was added and thereaction temperature was kept at 110° C. for 5 hours. After the reactionwas cooled to 60° C., toluene (80 mL) was further added. The solutionwas precipitated into 300 mL of hexane. After filtration and washingwith ethyl acetate (100 mL×3×) and drying in vaccuo, a white polymer(40.5 g) was obtained. ¹H NMR showed 8% hydrophobe incorporation. TheBrookfield viscosity of a 5% aqueous solution of this oligomer was124,000 cps (BF LV, S-63, 0.3 rpm at 25° C.). Paint performance: SG10 M(standard formulation). TE %=0.14, Viscosity Loss upon Tinting (VLT)=−6KU. For UCAR 379 G, TE %=0.68, VLT=−13 KU.

EXAMPLE 3 PEG 35K, 10.4% Addition Level of glycidyl 2 methyl phenylether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch and a heatingmantle, a mixture of 30 g of 35,000 Mw PEG (0.0015 mol) and toluene (80mL) was heated to 60° C. At this temperature, KOH (1.15 g, 0.02 mol, in3 g of water) was added and the reaction mixture was stirred for 1 hour.Glycidyl 2-methyl phenyl ether (3.38 g, 0.02 mole) was added and thereaction temperature was kept at 110° C. for 5 hours. After the reactionmass was cooled to 60° C., toluene (80 mL) was further added. Thesolution was precipitated into 300 mL of hexane. After filtration andwashing with ethyl acetate (100 mL×3×) and drying in vaccuo, a whitepowder polymer (31 g) was obtained. ¹H NMR showed 6.8% hydrophobeincorporation. The Brookfield viscosity of a 5% aqueous solution of thisoligomer was 184,000 cps (BF LV, S-63, 0.3 rpm at 25° C.). Paintperformance: SG10 M (standard formulation) TE %=0.11, Viscosity Lossupon Tinting (VLT)=−12 KU. For UCAR 379 G, TE %=0.57, VLT=−11 KU.

EXAMPLE 4 PEG 20K, 14% of glycidyl 2 methyl phenyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 20,000 Mw PEG (0.0015 mol) and toluene (80mL) was heated to 60° C. At this temperature, KOH (3.37 g, 0.06 mol, in3 g of water) was added and the reaction mixture was stirred for 1 hour.Glycidyl 2-methyl phenyl ether (4.93 g, 0.03 mole) was added and thereaction temperature was kept at 110° C. for 5 hours. After the reactionwas cooled to 60° C., toluene (80 mL) was further added. The solutionwas precipitated into 300 mL of hexane. After filtration and washingwith ethyl acetate (100 mL×3×) and drying in vacuum, a white powderpolymer (33 g) was obtained. The Brookfield viscosity of a 5% aqueoussolution of this oligomer was 37,200 cps (BF LV, S-63, 0.3 rpm at 25°C.). Paint performance: SG10 M (standard formulation) TE %=0.12,Viscosity Loss upon Tinting (VLT)=−7 KU. For UCAR 379 G, TE %=0.47,VLT=−8 KU.

EXAMPLE 5 PEG 30K, 27% Addition Level of glycidyl 2 methyl phenyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 12,000 Mw PEG (0.0015 mol) and toluene (80mL) was heated to 60° C. At this temperature, KOH (1.7 g, 0.03 mol, in 3g of water) was added and the reaction mixture was stirred for 1 hour.Glycidyl 2-methyl phenyl ether (10.9 g, 0.02 mole) was added and thereaction temperature was kept at 110° C. for 5 hours. After the reactionmass was cooled to 60° C., toluene (80 mL) was further added. Thesolution was precipitated into 300 mL of hexane. After filtration andwashing with ethyl acetate (100 mL×3×) and drying in vacuum, a whitepowder polymer (35 g) was obtained. ¹H NMR showed 20% hydrophobeincorporation. The Brookfield viscosity of a 5% aqueous solution of thisoligomer was a gel. Paint performance: SG10 M (standard formulation):Not soluble in the paint. For UCAR 379 G, TE %=0.57, VLT=−1 KU.

EXAMPLE 6 PAPE 35K, 6.9% Addition Level of butyl-glycidyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 35,000 Mw PAPE and toluene (80 mL) washeated to 60° C. At this temperature, KOH (0.95 g, 0.02 mol, in 1 g ofwater) was added and the reaction mixture was stirred for 1 hour. Butylglycidyl ether (2.23 g, 0.02 mole) was added and the reactiontemperature was kept at 110° C. for 5 hours. After the reaction mass wascooled to 60° C., toluene (80 mL) was further added. The solution wasprecipitated into 300 mL of hexane. After filtration and washing withethyl acetate (100 mL×3×) and drying in vacuum, a white polymer (30 g)was obtained. ¹H NMR showed 4.7% hydrophobe incorporation. The viscosityof a 5% aqueous solution of this oligomer was >200,000 cps (BF LV, S-63,0.3 rpm at 25° C.). Paint performance: SG10 M (standard formulation). TE%=0.11, Viscosity Loss upon Tinting (VLT)=−30 KU. For UCAR 379 G, TE%=0.47, VLT=−35 KU.

EXAMPLE 7 PEG 20K, 16.3% Addition Level of butyl-glycidyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 20,000 Mw PEG (0.0015 mol) and toluene (80mL) was heated to 60° C. At this temperature, KOH (0.77 g, 0.015 mol, in1 g of water) was 10 added and the reaction mixture was stirred for 1hour. Butyl glycidyl ether (5.86 g, 0.045 mole) was added and thereaction temperature was kept at 110° C. for 5 hours. After the reactionmass was cooled to 60° C., toluene (80 mL) was further added. Thesolution was precipitated into 300 mL of hexane. After filtration andwashing with ethyl acetate (100 mL×3×) and drying in vaccuo, a whitepolymer (31 g) was obtained. ¹H NMR showed 9.5% hydrophobeincorporation. Paint performance: SG10 M (standard formulation) notdissolved in the paint. For UCAR 379 G, TE %=0.40, VLT=3 KU.

EXAMPLE 8 PEG 35K, 8.2% Addition Level of butyl-glycidyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 35,000 Mw PEG and toluene (80 mL) washeated to 60° C. At this temperature, KOH (0.77 g, 0.02 mol, in 1 g ofwater) was added and the reaction mixture was stirred for 1 hour. Butylglycidyl ether (2.68 g, 0.02 mole) was added and the reactiontemperature was kept at 110° C. for 5 hours. After the reaction mass wascooled to 60° C., toluene (80 mL) was further added. The solution wasprecipitated into 300 mL of hexane. After filtration and washing withethyl acetate (100 mL×3×) and drying in vaccuo, a white polymer (33 g)was obtained. ¹H NMR showed 7.3% hydrophobe incorporation. Thebrookfield viscosity of a 5% aqueous solution of this oligomer was836,000 cps (BF LV, S-63, 0.3 rpm at 25° C.). Paint performance: SG10 M(standard formulation). TE %=0.15, Viscosity Loss upon Tinting (VLT)=−21KU. For UCAR 379 G, TE %=0.32, VLT=−37 KU.

EXAMPLE 9 PEG 35K, 6% Addition Level of 2-ethyl hexyl-glycidyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 35,000 Mw PEG and toluene (80 mL) washeated to 60° C. At this temperature, KOH (0.77 g, 0.02 mol, in 1 g ofwater) was added and the reaction mixture was stirred for 1 hour.2-Ethyl hexyl glycidyl ether (1.91 g, 0.02 mole) was added and thereaction temperature was kept at 110° C. for 5 hours. After the reactionmass was cooled to 60° C., toluene (80 mL) was further added. Thesolution was precipitated into 300 mL of hexane. After filtration andwashing with ethyl acetate (100 mL×3×) and drying in vacuum, a whitepolymer (31 g) was obtained. ¹H NMR showed 5.2% hydrophobeincorporation. The Brookfield viscosity of a 5% aqueous solution of thisoligomer was >200,000 cps (BF LV, S-63, 0.3 rpm at 25° C.). Paintperformance: SG10 M (standard formulation). TE %=0.11, Viscosity Lossupon Tinting (VLT)=−24 KU. For UCAR 379 G, TE %=0.28, VLT=−30 KU.

EXAMPLE 10 PEG 10K, 16.2% Addition Level of C12 glycidyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 10,000 Mw PEG and toluene (80 mL) washeated to 60° C. At this temperature, KOH (1.52 g, 0.04 mol, in 1.5 g ofwater) was added and the reaction mixture was stirred for 1 hour.Dodecyl glycidyl ether (5.81 g, 0.024 mole) was added and the reactiontemperature was kept at 110° C. for 5 hours. After the reaction mass wascooled to 60° C., toluene (80 mL) was further added. The solution wasprecipitated into 300 mL of hexane. After filtration and washing withethyl acetate (100 mL×3×) and drying in vacuum, a white polymer (31.8 g)was obtained. ¹H NMR showed 11% hydrophobe incorporation. The Brookfieldviscosity of a 5% aqueous solution of this oligomer was >400000 cps (BFLV, S-63, 0.3 rpm at 25° C.). Paint performance: SG10 M (standardformulation). The material was not soluble in this paint. For UCAR 379G, TE %=0.52, VLT=−17 KU.

EXAMPLE 11 PEG 10K, 23% Addition Level of C12 glycidyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 10,000 Mw PEG and toluene (80 mL) washeated to 60° C. At this temperature, KOH (2.19 g, 0.04 mol, in 2 g ofwater) was added and the reaction mixture was stirred for 1 hour.Dodecyl glycidyl ether (8.71 g, 0.04 mole) was added and the reactiontemperature was kept at 110° C. for 5 hours. After the reaction mass wascooled to 60° C., toluene (80 mL) was further added. The solution wasprecipitated into 300 mL of hexane. After filtration and washing withethyl acetate (100 mL×3×) and drying in vaccuo, a white polymer,(33 g)was obtained. ¹H NMR showed 11% hydrophobe incorporation. The Brookfieldviscosity of a 5% aqueous solution of this oligomer was >200,000 cps (BFLV, S-63, 0.3 rpm at 25° C.). Paint performance: SG10 M (standardformulation). The material was not soluble in this paint. For UCAR 379G, TE% =0.52, VLT=−6 KU.

EXAMPLE 12 PEG 20K, 7.2% Addition Level of C12 epoxide

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 20,000 Mw PEG and toluene (80 mL) washeated to 60° C. At this temperature, KOH (0.67 g, 0.04 mol, in 1 g ofwater) was added and the reaction mixture was stirred for 1 hour.1,2-Epoxydodecane (2.33 g, 0.012 mole) was added and the reactiontemperature was kept at 110° C. for 5 hours. After the reaction mass wascooled to 60° C., toluene (80 mL) was further added. The solution wasprecipitated into 300 mL of hexane. After filtration and washing withethyl acetate (100 mL×3×) and drying in vacuum, a white polymer (31 g)was obtained. ¹H NMR showed 6% hydrophobe incorporation. The Brookfieldviscosity of a 5% aqueous solution of this oligomer was >400,000 cps (BFLV, S-63, 0.3 rpm at 25° C.). Paint performance: SG10 M (standardformulation). The material was not soluble in this paint. For UCAR 379G, TE %=0.38, VLT=−24 KU.

EXAMPLE 13 PEG 12K, 8.4% Addition Level of C12 epoxide

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 30 g of 12,000 Mw PEG and toluene (80 mL) washeated to 60° C. At this temperature, KOH (0.84 g, 0.015 mol, in 1 g ofwater) was added and the reaction mixture was stirred for 1 hour.1,2-Epoxydodecane (2.33 g, 0.012 mole) was added and the reactiontemperature was kept at 110° C. for 5 hours. After the reaction mass wascooled to 60° C., toluene (80 mL) was further added. The solution wasprecipitated into 300 mL of hexane. After filtration and washing withethyl acetate (100 mL×3×) and drying in vacuum, a white polymer (31.2 g)was obtained. ¹H NMR showed 7.3% hydrophobe incorporation. The viscosityof a 5% aqueous solution of this oligomer was >400,000 cps (BF LV, S-63,0.3 rpm at 25° C.). Paint performance: SG10 M (standard formulation).The material was not soluble in this paint. For UCAR 379 G, TE %=0.49,VLT=−4 KU.

EXAMPLE 14 PAPE, 22% of glycidyl 2 methyl phenyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 50 g of 4,000 Mw PEG (0.012 mol) and NaOH pellets(3 g) was heated at 80° C. for 1 hour. At this temperature,dibromo-methane (1.65 g, 9.4 mmol) was added and the reaction mixturewas stirred for 4 hours. Glycidyl 2-methyl phenyl ether (14.23 g, 0.09mole) was added and the reaction temperature was kept at 110° C. for 5hours. After the reaction mass was cooled to 60° C., toluene (100 g) wasfurther added. The solution was precipitated into 300 mL of hexane.After filtration and washing with ethyl acetate (100 mL×3×) and dryingin vacuum, a white powder polymer (50 g) was obtained. ¹H NMR showed14.9% hydrophobe incorporation. The Brookfield viscosity of a 5% aqueoussolution of this oligomer was 58,800 cps. The Brookfield viscosity of a25% solution in 25% butyl carbitol was 1,500 cps (BF LV, S-63, 0.3 rpmat 25° C.). Paint performance: SG10 M (standard formulation). TE %=0.30.Viscosity Loss upon Tinting (VLT)=3 KU.

EXAMPLE 15 PAPE, 16% of glycidyl 2 methyl phenyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 40.6 g of 4,000 Mw PEG (0.01 mol) and NaOH pellets(1.6 g) was heated at 80° C. for 1 hour. At this temperature,dibromo-methane (1.32 g, 7.5 mmol) was added and the reaction mixturewas stirred for 4 hours. Glycidyl 2-methyl phenyl ether (7.22 g) wasadded and the reaction temperature was kept at 110° C. for 5 hours.After the reaction mass was cooled to 60° C., toluene (130 g) wasfurther added. The solution was precipitated into 300 mL of hexane.After filtration and washing with ethyl acetate (100 mL×3×) and dryingin vaccuo, a white powder polymer (45.5 g) was obtained. ¹H NMR showed10.9% hydrophobe incorporation. The Brookfield viscosity of a 5% aqueoussolution of this oligomer was 19,000 cps. The Brookfield viscosity of a25% solution in 25% butyl carbitol was 684 cps (BF LV, S-63, 0.3 rpm at25° C.). Paint performance: SG10 M (standard formulation). TE %=0.25,Viscosity Loss upon Tinting (VLT)=−1 KU. For UCAR 379 G, TE %=0.63,VLT=−8 KU.

EXAMPLE 16 PEG 20K, 15% of glycidyl 2 methyl phenyl ether

In a 250 mL, round bottom 3-neck flask equipped with a condenser, anitrogen in/out let, a mechanical stirrer, a thermo-watch, and a heatingmantle, a mixture of 20 g of 20,000 Mw PEG (0.0015 mol) and toluene (120g) was heated to 60° C. At this temperature, KOH (3.4 g, 0.06 mol, in3.4 g of water) was added and the reaction mixture was stirred for 1hour. Glycidyl 2-methyl phenyl ether (9.12 g, 0.055 mole) was added andthe reaction temperature was kept at 110° C. for 5 hours. After thereaction mass was cooled to 60° C., toluene (80 mL) was further added.The solution was precipitated into 300 mL of hexane. After filtrationand washing with ethyl acetate (100 mL×3×) and drying in vaccuo, a whitepowder polymer (56 g) was obtained. The viscosity of a 5% aqueoussolution oligomer was 211,600 cps (BF LV, S-63, 0.3 rpm at 25° C.).Paint performance: SG10 M (standard formulation) TE %=0.18, ViscosityLoss upon Tinting (VLT)=−1 KU. For UCAR 379 G, TE %=0.61, VLT=−5 KU.

The Examples above are summarized in the following Table 1, and comparedto the control of commercially available thickener, NLS 200.

TABLE 1 Paint performance for some thickeners Hydrophobe Backbone KU TESamples type Type HM % TE %1 loss %2 Control C16 PAPE 2% 0.11 −48 0.56Example 1 MPGE PEG, 20K 12%  0.11 −4 0.54 2 MPGE PEG, 35K 8% 0.14 −60.68 3 MPGE PEG, 35K 7% 0.11 −12 0.57 4 MPGE PEG, 20K 9% 0.12 −7 0.47 5MPGE PEG, 30K 20%  Insol. na 0.57 6 BGE PAPE, 35K 5% 0.11 −30 0.47 7 BGEPEG, 20K 10%  Insol. na 0.4 8 BGE PEG, 35K 7% 0.15 −21 0.32 9 EHGE PEG,35K 5% 0.11 −24 0.28 10 C12GE PEG, 10K 15%  Insol. na 0.52 11 C12GE PEG,10K 16%  Insol. na 0.52 12 C12E PEG, 20K 6% Insol. na 0.38 13 C12E PEG,12K 7% Insol. na 0.49 14 MPGE PAPE, 16K 15%  0.3 3 0.3 15 MPGE PAPE, 20K11%  0.25 1 0.63 16 MPGE PEG, 20K 10%  0.18 −1 0.61 MPGE: Methyl PhenylGlycidyl Ether BGE: Butyl Glycidyl Ether EHGE: Ethyl Hexyl GlycidylEther C12GE: Dodecyl Glycidyl Ether C12E: 1,2 Epoxide Dodecane PAPE:Polyacetal Polyether PEG: Polyethyleneglycol TE %: Thickening efficiency

EXAMPLE 17 Hydrophobically Modified Polyurethane

A mixture of PEG (40 g, Mw=8,000), toluene (50 mL) and 4,4′methylenebis(cyclohexyl isocyanate) (0.9 g) and dibutyltinlaurate (10 mg) washeated together at 80° C. for 16 hours. Methylphenylglycidyl ether (8 g)and NaOH (1 g) were added to the mixture and the reaction was kept at120° C. for 2 hours. The polymer was precipitated in hexane. Afterdrying, 40 g of a polymer product was obtained (hydrophobe content=2%,Mw=15,000)

EXAMPLE 18 Hydrophobicallly Modified Branched PAPE

A mixture of PEG (40 g, 4,000 Mw), trimethylolpropane ethoxylate (0.4g), and NaOH (2.4 g) was kept at 80° C. for 1 hour. Dibromomethane (1.8g) and toluene (30 mL) were added and the mixture was kept at 80° C. for4 hours. Methylphenylglycidyl ether (4.87 g) was added to the reactionand the temperature was raised to 1,200° C. After 4 hours, the reactionwas stopped. Toluene (120 mL) was added to dilute the reaction content.The product was isolated by precipitation in hexane (300 mL) and washingwith ethyl acetate. After drying, a polymer (46 g) was obtained. A 5%solution of this material had a Brookfield viscosity of 22,000 cps.Thickening efficiency of this material in SG10M was 0.13. Viscosity lossupon tinting was −23 KU.

EXAMPLE 19 Hydrophobically Modified diisocyanate

A mixture of PEG (60 g, Mw=4,000) was heated with isopheronediisocyanate (1.8 g) and 2 drops of dibutyltinlaurate at 80° C. for 6hours; then NaOH (1 g) was added. After 1 hour, methylphenylglycidylether (6 g) was added. The mixture was heated at 120° C. for 4 hours. Apolymer was obtained.

Di-hydroxyl telechelic product of the above process may be furtherreacted to increase its molecular weight by the addition of couplingreagents bearing two or more hydroxyl reactive groups to make linear orbranched polymers that have multiple hydrophobic sections. Typically,di-, tri- or tetra functional compounds used are dihalide, diepoxide,di-urethane, tri-halide, triepoxide, tri-isocyanate. Di-functionalcoupling molecules would give linear products and polyfunctionalcoupling molecules would give branched or dendritic products. Each typeof product may give advantage for a specific need.

EXAMPLE 20 Linear Coupling using a diisocyanate

A mixture of PEG (600 g, Mw=8,000) was heated with NaOH (12 g) anddibromomethane (8,5 g) at 80° C. for 1 hour; then methyl phenyl glycidylether (107 g) was added and heated for 3 hours at 120° C. A polymerproduct was obtained (Mn=22,000, hydrophobe content 8.2%) afterpurification by using toluene and hexane. A solution of this polymer (10g) in toluene (100 mL) was heated with methylene-bis-phenylisocyanate(1.1 g) at 60° C. for 24 hours. A polymer was obtained afterprecipitation in hexane. The polymer has the number average molecularweight (Mn) of 53,000.

EXAMPLE 21 Linear Coupling using dibromomethane

A mixture of PEG (60 g, Mw=8,000), NaOH (1.2 g), andmethylphenylglycidyl ether (8 g) was heated together at 120° C. for 3hours to give a telechelic oligomer of Mn=9,000. To this reactionmixture of oligomer, dibromomethane (1.6 g) was added at 80° C. After 1hour, a polymer (62 g) of a number average molecular weight of 19,000was obtained.

EXAMPLE 22 Linear Coupling using PAPE

A mixture of PEG (27 g, Mw=4,000), NaOH (0.7 g), and methylphenylglycidylether (6 g) was heated to 120° C. for 2 hours. After the mixturewas cooled to 80° C., NaOH (1.5 g), dibromomethane (1.1 g), and PEG (23g, Mw=4,000) were added and stirred together for 2 hours. Aftercoagulation in hexane and drying, a polymer of Mw=13,000 was collected(52 g). The hydrophobe content was 2%.

In the above Examples, hydrophobes of this invention were built stepwiseon the polymer backbone. It is possible to, also, pre-form thehydrophobes of this invention and link them to the polymer backbone ofinterest like those from isocyanate (HEUR type), cellulosic,acrylate/acrylamide (HASE type), polyvinyl alcohol chemistries asdescribed in the previous section.

It is also possible to use a polymerizable monomer containinghydrophobes of this invention to make different products by polymerizingwith other monomers. Polymerizable monomers could be of double bond innature (like vinyl, maleate, acrylate, acrylamide . . . ), or ringopening in nature (like epoxide, oxazoline, cyclic oxide, cycliccarbonate . . . ). Polymerizable monomers could also be monomers thatcould participate in a condensation polymerization like a diacid,diester, diol, diamine, dialkyihalides.

EXAMPLE 23 Polystyrene-Terminated PEG

Polystyrene-terminated PEG was synthesized by atom transfer radicalpolymerization (ATRP). Macroinitiators for ATRP were synthesized byreactions of PEGs (Mw of 8,000, 20,000, 35,000) and2-chloro-2-phenylacetyl chloride. Then styrene was polymerized in thepresence of the macroinitiator to produce polystyrene-terminated PEG, asshown in scheme 2.

ATRP is a newly developed radical polymerization technique. In the ATRPa transition metal compound acts as a carrier of a halogen atom in areversible redox process. Its living characteristic allows theincorporation of styrene increasing linearly with time of thepolymerization. Several polystyrene-terminated PEG were synthesized fromPEG with different molecular weight and with different length of thepolystyrene segment, as listed in Table 2.

TABLE 2 Synthesis of Polystyrene-terminated PEG Number of DesignationPEG (Mw) Phenyl/Each End Viscosity² cps, (T.S.) A 20,000 6 100,000(3.5%) B 8,000 5 11,800 (4.0%) C 35,000 4 34,000 (5.0%) D 20,000 4 420(5.0%) E 8,000 9 Poor solubility F¹ 8,000 5 13,000 (4.0%) ¹Repeat of B.²Brookfield viscosity was measured at 22° C.

¹H NMR was used to determine the incorporation of phenyl at each end forthese triblock polymers after recrystallization to remove small amountof homopolystyrene. The triblock polymer with PEG of 8,000 and 9 phenylsat each end shows limited solubility. The triblock polymer with PEG of20,000 Mw and 4 phenyls at each end shows low viscosity at 5.0% solids.

Paint evaluation of these triblock polymers was carried out in both UCAR379 G and SG 10M semi-gloss paints. The results are listed in Table 3and Table 4.

TABLE 3 UCAR 379 Semi-Gloss Paint Evaluation of Polystyrene-TerminatedPEG Efficiency #/100 Stormer ICI Lev Sag Gloss ΔKU Designation gallonWt. % Ini eq P 0-10 mil 60 Ini eq A 7.01 0.66 114 102 0.423 0 24 61 −12−12 B 8.00 0.76 85 83 0.308 6 8 50 — −7 C 10.01 0.95 89 88 0.548 5 8 60— −13 D&C Mixture¹ 12.00 1.14 80 81 0.548 6 6 63 — −6 ¹Weight ratio ofthis mixture is 4/1.

TABLE 4 SG-10M Semi-Gloss Paint Evaluation of Polystyrene-Terminated PEGEfficiency #/100 Stormer ICI Lev Sag Gloss ΔKU Designation gallon Wt. %Ini eq P 0-10 mil 60 ini eq A 2.10 0.20 96 97 0.252 0 24 27 −5 −2 B 2.120.20 94 93 0.254 0 24 18 3 4 C 1.80 0.17 91 91 0.267 0 22 50 −5 −8 D&Cmixture 3.60 0.34 96 95 0.379 0 24 57 −6 −5

The application of the product of this invention is not restricted forpaint (as demonstrated) but it could be in any applications where twonon-compatible phases meet (like oil/water, hydrophobicsurface/hydrophilic surface, high surface tension/low surface tensioncontact). Typical applications may be from dispersion stabilization,emulsion stabilization, emulsion polymerization, paper making drainageaid, paper coating, paper sizing, pitch control in pulping, degreasingformulation, hair care/skin care gel, oil field fluids, concreterheology control, ceramic green body additive, thermoplastic blends andsurface modification.

Although the invention has been illustrated by the above Examples, thisis not to be construed as being limited thereby, but rather, theinvention encompasses the generic area as hereinbefore disclosed.Various modifications and embodiments can be made without departing fromthe spirit and scope of the invention.

1. A polymer composition comprising a water soluble or water swellablesynthetic polymer backbone hydrophobically modified with oligomerichydrophobes having covalently connected ends and/or intermediate blocksof oligomeric hydrophobes that have the following formula:

where: a) n is an integer from 1-100 b) R is CH ₂OC₈H₁₇, c) A is theconnecting diradical —O—CH₂—, d) B is the connecting group —O—CH₂—, e) Cis a connecting end same as A or a terminating end equal to: —OH,wherein the water soluble or water swellable synthetic polymer backboneis polyacetalpolyether.
 2. The composition of claim 1, wherein n has alower limit of
 3. 3. The composition of claim 1, wherein n has a lowerlimit of
 7. 4. The composition of claim 1, wherein n has a lower limitof
 10. 5. The composition of claim 1, wherein n has an upper limit of75.
 6. The composition of claim 1, wherein n has an upper limit of 50.7. The composition of claim 1, wherein n has an upper limit of
 20. 8. Aprocess for preparing the water soluble or water swellable polymercomposition comprising a) reacting a water soluble or water swellablebackbone with a catalyzing agent in order to activate the polymerbackbone and produce a reaction mass, b) adding an oligomerizinghydrophobic monomer(s) to the reaction mass, and c) polymerizing thereaction mass at sufficient temperature and for a sufficient time inorder to add the oligomerizing hydrophobic monomer(s) to the backbone asend groups and/or intermediate groups to obtain the water soluble orwater swellable polymer composition, wherein the backbone ispolyacetalpolyether and wherein the water soluble or water swellablepolymer composition has covalently connected ends and/or intermediateblocks of oligomeric hydrophobes that have the following formula: where:

i) n is an integer from 1-100 ii) R is CH₂OC₈H₁₇, iii) A is theconnecting diradical —O—CH₂—, iv) B is the connecting group —OCH₂—, andv) C is a connecting end same as A or a terminating end equal to; —OH.9. The process of claim 8, wherein the polymer prepared by the processhas a weight average molecular weight with an upper limit of about10,000,000.
 10. The process of claim 8, wherein the polymer prepared bythe process has a weight average molecular weight with an upper limit ofabout 1,000,000.
 11. The process of claim 8, wherein the polymerprepared by the process has a weight average molecular weight with anupper limit of about 100,000.
 12. The process of claim 8, wherein thepolymer prepared by the process has a weight average molecular weightwith a lower limit of about
 400. 13. The process of claim 8, wherein thepolymer prepared by the process has a weight average molecular weightwith a lower limit of about
 1000. 14. The process of claim 8, whereinthe polymer prepared by the process has a weight average molecularweight with a lower limit of about
 4000. 15. The process of claim 8,wherein the polymer prepared by the process has intermediate blocks ofoligomeric hydrophobes that are pendant of the backbone.
 16. The processof claim 8, wherein the polymer prepared by the process has intermediateblocks of oligomeric hydrophobes that are internal in the backbone. 17.An aqueous protective coating composition comprising (a) the compositionof claim 1, (b) a colorant, and (c) a film forming latex, wherein theviscosity of the coating composition remains unchanged or has aninsignificant loss as compared to when using conventional rheologymodifiers upon adding a colorant.
 18. The aqueous protective coatingcomposition of claim 17, wherein the composition is a latex paint. 19.The aqueous protective coating composition of claim 17, wherein thelatex is selected from the group consisting of acrylics, vinyl acrylics,and styrene.
 20. The aqueous protective coating composition of claim 19,wherein the latex paint has a pigment volume concentration of from about15 to about
 80. 21. An aqueous protective coating composition comprisinga) the polymer composition of claim 1, b) at least one thickenerselected from the group consisting of hydrophobically modified ethyleneoxide urethane block copolymers, hydrophobically modified alkalinesoluble emulsions, cellulose derivative, and polyacetalpolyether, c) acolorant, and d) a film forming latex.
 22. The aqueous protectivecoating composition of claim 21, wherein the cellulose derivative ispresent and is selected from the group consisting ofhydroxyethylcellulose (HEC), hydroxypropyl cellulose (HPC),methylcellulose (MC), carboxymethylcellulose (CMC), methylhydroxyethylcellulose (MHEC), ethylhydroxyethylcellulose (EHEC), andhydrophobically modified hydroxyethylcellulose (HMHEC).